Synthesis, characterization, and crystal structures of nickel complexes derived from N,N'-bis(3,5-dichlorosalicylidene)-1,3-pentanediamine and N,N'-bis(3-methylsalicylidene)-1,2-ethanediamine

Article abstract of DOI:10.1080/15533174.2013.791850

Two new mononuclear Schiff base nickel(II) complexes, [Ni(ClSal)] (1) and [Ni(MeSal)] (2) (H₂ClSal = N,N'-bis(3,5-dichlorosalicylidene)-1,3- pentanediamine; H₂MeSal = N,N'-bis(3-methylsalicylidene)-1,2- ethanediamine), have been synt

Full text of DOI:10.1080/15533174.2013.791850

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Synthesis, Characterization, and Crystal Structures
of Nickel Complexes Derived from N,N′-Bis(3,5-
dichlorosalicylidene)-1,3-pentanediamine and N,N′-
Bis(3-methylsalicylidene)-1,2-ethanediamine
Gui-Hua Sheng a , Xiao-Shan Cheng b , Xue Wang b , Di Huang b , Zhong-Lu You b & Hai-Liang
Zhu a
a School of Life Sciences , Shandong University of Technology , ZiBo , P. R. China
b Department of Chemistry and Chemical Engineering , Liaoning Normal University , Dalian ,
116029 , P. R. China
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Accepted author version posted online: 12 Jul 2013.Published online: 25 Feb 2014.
To cite this article: Gui-Hua Sheng , Xiao-Shan Cheng , Xue Wang , Di Huang , Zhong-Lu You & Hai-Liang Zhu (2014)
Synthesis, Characterization, and Crystal Structures of Nickel Complexes Derived from N,N′-Bis(3,5-dichlorosalicylidene)-1,3-
pentanediamine and N,N′-Bis(3-methylsalicylidene)-1,2-ethanediamine, Synthesis and Reactivity in Inorganic, Metal-Organic,
and Nano-Metal Chemistry, 44:6, 864-867, DOI: 10.1080/15533174.2013.791850
To link to this article: http://dx.doi.org/10.1080/15533174.2013.791850
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 44:864–867, 2014
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2013.791850
Synthesis, Characterization, and Crystal Structures
of Nickel Complexes Derived from
N,Nꢀ-Bis(3,5-dichlorosalicylidene)-1,3-pentanediamine
and N,Nꢀ-Bis(3-methylsalicylidene)-1,2-ethanediamine
Gui-Hua Sheng,1 Xiao-Shan Cheng,2 Xue Wang,2 Di Huang,2 Zhong-Lu You,2
and Hai-Liang Zhu1
1School of Life Sciences, Shandong University of Technology, ZiBo, P. R. China
2Department of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029,
P. R. China
edge, no complexes have been reported from the Schiff base
ligand N,Nꢁ-bis(3,5-dichlorosalicylidene)-1,3-pentanediamine
(H2ClSal; Scheme 1), and two complexes have been reported
from the Schiff base ligand N,Nꢁ-bis(3-methylsalicylidene)-1,2-
ethanediamine (H2MeSal; Scheme 1).[14,15] As an extension of
our work on Schiff base complexes, we report in this article
the syntheses, characterization, and crystal structures of new
mononuclear Schiff base nickel(II) complexes, [Ni(ClSal)] (1)
and [Ni(MeSal)] (2).
Two new mononuclear Schiff base nickel(II) complexes,
[Ni(ClSal)] (1) and [Ni(MeSal)] (2) (H2ClSal = N,Nꢀ-bis(3,5-
dichlorosalicylidene)-1,3-pentanediamine; H2MeSal = N,Nꢀ-bis(3-
methylsalicylidene)-1,2-ethanediamine), have been synthesized
and characterized by elemental analyses, infrared spectra, and
single-crystal X-ray diffraction. Complex 1 crystallizes in the or-
thorhombic space group P212121, with unit cell dimensions a =
9.788(1) Å, b = 10.206(1) Å, c = 20.458(2) Å, V = 2043.7(4) Å3,
Z = 4, R1 = 0.0814, and wR2 = 0.1689. Complex 2 crystallizes in
the monoclinic space group P21/n, with unit cell dimensions a =
11.6353(5) Å, b = 11.8807(6) Å, c = 12.8241(6) Å, β = 115.213(1)◦,
V = 1603.9(1) Å3, Z = 4, R1 = 0.0243, and wR2 = 0.0675. The
Ni atoms in the complexes are four-coordinated in square planar
geometry by the N2O2 donor set of the ligands.
Keywords Crystal structure, mononuclear, nickel complex, Schiff
SCH. 1. The Schiff base ligands H2ClSal (left) and H2MeSal (right).
base
INTRODUCTION
EXPERIMENTAL
Schiff bases and their transition metal complexes have at-
tracted much attention for their importance in the fields of
coordination chemistry related to catalysis and enzymatic re-
actions, magnetism, and molecular architectures.[1–5] Nickel
is an important element in biological systems, which func-
tions as the active site of hydrolytic enzymes, such as ure-
ase.[6] Nickel complexes with Schiff bases have been proved
to possess interesting biological activities.[7–10] Recently, we
have reported some Schiff base complexes.[11–13] To our knowl-
Materials and Measurements
Commercially available 3,5-dichlorosalicylaldehyde, 3-
methylsalicylaldehyde, pentane-1,3-diamine, and ethane-1,2-
diamine were purchased from Aldrich and used without further
purification. Other solvents and reagents were made in China
and used as received. C, H, and N elemental analyses were per-
formed with a Perkin-Elmer elemental analyzer. The infrared
spectra were recorded on a Nicolet AVATAR 360 spectrometer
as KBr pellets in the 4000–400 cm−1 region.
Synthesis of the Schiff Base H2ClSal
Received 19 March 2013; accepted 27 March 2013.
3,5-Dichlorosalicylaldehyde (2.0 mmol, 0.382 g) and pentan-
1,3-diamine (1.0 mmol, 0.102 g) were dissolved in EtOH
(20 mL) with stirring. The mixture was stirred for about 30 min
at room temperature to give a large quantity of yellow precip-
itate. The product was filtered, washed with cold ethanol, and
Address correspondence to Zhong-Lu You, Department of Chem-
istry and Chemical Engineering, Liaoning Normal University, Dalian
116029, P. R. China. E-mail: youzhonglu@yahoo.com.cn and Hai-
Liang Zhu, School of Life Sciences, Shandong University of Technol-
ogy, ZiBo 255049, P. R. China. E-mail: hailiang zhu@163.com
864

NICKEL COMPLEXES
865
TABLE 1
Crystallographic and experimental data for the complexes
TABLE 2
Selected bond lengths (Å) and angles (◦)
Complexes
1
2
1
Ni(1)-O(1)
Ni(1)-N(1)
O(1)-Ni(1)-
O(2)
O(2)-Ni(1)-
N(2)
1.815(6)
Ni(1)-O(2)
1.830(6)
1.877(7)
94.4(3)
Formula
FW
Crystal shape/color
Crystal size/ mm
Crystal system
Space group
a/Å
b/Å
C19H16Cl4N2NiO2
504.8
C18H18N2NiO2
353.0
1.895(8) Ni(1)-N(2)
82.2(3)
O(1)-Ni(1)-
N(2)
block/red
block/red
0.15 × 0.15 × 0.13 0.20 × 0.17 × 0.15
166.8(3) O(1)-Ni(1)-
N(1)
93.9(3)
165.4(3)
92.4(3)
Orthorhombic
P212121
Monoclinic
P21/n
O(2)-Ni(1)-
N(1)
N(2)-Ni(1)-
N(1)
9.788(1)
10.206(1)
20.458(2)
11.635(1)
11.881(1)
12.824(1)
115.213(1)
1603.9(1)
4
298(2)
1.220
1.462
2982/208
0
c/Å
2
β/◦
Ni(1)-O(1)
Ni(1)-N(1)
O(1)-Ni(1)-
O(2)
O(2)-Ni(1)-
N(2)
1.842(1) Ni(1)-O(2)
1.847(1) Ni(1)-N(2)
84.9(1)
1.844(1)
1.847(1)
177.0(1)
V/Å3
2043.7(4)
4
Z
T/K
O(1)-Ni(1)-
N(2)
O(1)-Ni(1)-
N(1)
298(2)
1.490
1.641
μ/mm−1(Mo Kα)
Dc/g cm−3
94.3(1)
94.7(1)
86.2(1)
Reflections/parameters 4181/254
Restraints
Index ranges/h, k, l −11, 12; −12, 12; −14, 12; −14, 9;
O(2)-Ni(1)-
N(1)
178.2(1) N(2)-Ni(1)-
N(1)
0
−25, 25
−15, 15
Observed
reflections [I ≥
2σ(I)]
F(000)
Tmin
2718
2578
of H2Salpa (0.1 mmol, 44.8 mg) with stirring. The mixture was
stirred for 30 min at room temperature to give a red solution. The
resulting solution was allowed to stand in air for a week. Red
block-shaped crystals suitable for X-ray single-crystal analysis
were formed at the bottom of the vessel. The isolated prod-
uct was washed three times with cold EtOH, and dried in a
vacuum over anhydrous CaCl2. Yield, 63%. Anal. Calcd. for
C19H16Cl4N2NiO2: C, 45.2; H, 3.2; N, 5.5. Found: C, 45.1; H,
3.2; N, 5.4%.
1024
736
0.8074
0.8298
1.041
0.7924
0.8381
1.056
Tmax
Goodness of fit on
F2
R1, wR2 [I ≥
2σ(I)]a
0.0814, 0.1689
0.0243, 0.0675
R1, wR2 (all data)a
Largest diff. peak
and hole/e Å−3
ꢀ
0.1276, 0.1904
1.232, −0.956
0.0304, 0.0713
0.279, −0.186
Synthesis of [Ni(MeSal)]
An MeOH solution (5 mL) of Ni(MeCOO)2·4H2O
(0.1 mmol, 24.9 mg) was added to an MeOH solution (10 mL)
of H2MeSal (0.1 mmol, 29.6 mg) with stirring. The mixture
was stirred for 30 min at room temperature to give a red so-
lution. The resulting solution was allowed to stand in air for
a week. Red block-shaped crystals suitable for X-ray single-
crystal analysis were formed at the bottom of the vessel. The
isolated product was washed three times with cold EtOH, and
ꢀ
ꢀ
ꢀ
2
2 2
2 2 1/2
aR1 = ||Fo|−|Fc||/ |Fo|, wR2 = [ w(Fo −Fc ) / w(Fo ) ]
.
dried in vacuum. Yield, 87%. Anal. Calcd. for C19H18Cl4N2O2:
C, 50.9; H, 4.0; N, 6.2. Found: C, 50.7; H, 4.1; N, 6.3%.
Synthesis of H2MeSal
3-Methylsalicylaldehyde (2.0 mmol, 0.272 g) and ethane- dried in a vacuum over anhydrous CaCl2. Yield, 55%. Anal.
1,2-diamine (1.0 mmol, 0.060 g) were dissolved in EtOH Calcd. for C18H18N2NiO2: C, 61.2; H, 5.1; N, 7.9. Found: C,
(20 mL) with stirring. The mixture was stirred for about 30 min 61.1; H, 5.2; N, 8.1%.
at room temperature to give a large quantity of yellow precip-
Data Collection, Structural Determination,
and Refinement
Diffraction intensities for the complexes were collected at
298(2) K using a Bruker D8 VENTURE PHOTON diffrac-
tometer with Mo Kα radiation (λ = 0.71073 Å). The collected
itate. The product was filtered, washed with cold ethanol, and
dried in vacuum. Yield, 81%. Anal. Calcd. for C18H20N2O2: C,
73.0; H, 6.8; N, 9.4. Found: C, 73.1; H, 6.8; N, 9.5%.
Synthesis of [Ni(ClSal)]
An MeOH solution (5 mL) of Ni(MeCOO)2·4H2O data were reduced using the SAINT[16] and multi-scan absorp-
(0.1 mmol, 24.9 mg) was added to an MeOH solution (10 mL) tion corrections were performed using the SADABS.[17] The

866
G.-H. SHENG ET AL.
perpendicular angles, and from 165.4(3)◦ to 166.8(3)◦ (1) and
177.0(1)◦ to 178.2(1)◦ (2) for the trans angles. It can be seen that
the distortion of the coordination geometry in 1 is much more
severe than that in 2. The different degree of the distortion can
also be observed from the dihedral angles between the planes
defined by N(1)-Ni(1)-O(2) and O(1)-Ni(1)-N(2) in 1 (17.7(2)◦)
and N(1)-Ni(1)-O(1) and O(2)-Ni(1)-N(2) in 2 (3.3(2)◦). The
Ni-N and Ni-O bond lengths in both complexes are similar to
each other, and within normal values.[19,20] As for the Schiff
base ligands themselves, the dihedral angles between the two
benzene rings are 31.3(3)◦ for 1 and 5.9(3)◦ for 2.
IR Spectra
The IR spectra of the free Schiff bases and the complexes
provide information about the metal–ligand bonding. The bands
in the range of 2870–2960 cm−1 are characteristic of aliphatic
ν(C–H) vibrations for the complexes and the bands observed at
about 3050 cm−1 are attributed to the aromatic ν(C–H) vibra-
tions. The strong absorption bands at 1631 cm−1 for H2ClSal and
1626 cm−1 for H2MeSal are assigned to the azomethine groups,
ν(C=N).[21] The bands shift to lower wave numbers of 1608 and
1605 cm−1 for the complexes 1 and 2, respectively, which can
be attributed to the coordination of the nitrogen atoms of the
azomethine groups to the Ni atoms.[21] The phenolic ν(Ar–O)
in the free Schiff base ligands exhibits strong bands at about
1205 cm−1. However, in the complexes, the bands appear at
about 1180 cm−1, which may be assigned to the skeletal vi-
brations related to the phenolic oxygen of the Schiff base lig-
ands.[22] The weak bands located at the low wave numbers, from
450–550 cm−1, may be assigned to the ν(Ni–O) and ν(Ni–N).
FIG. 1. Molecular structure of 1 at 30% probability displacement.
structures were solved by direct methods and refined against F2
by full-matrix least-square methods using SHELXTL.[18] All of
the non-hydrogen atoms were refined anisotropically. All hydro-
gen atoms were placed in idealized positions and constrained
to ride on their parent atoms. The crystallographic data for the
complexes are summarized in Table 1. Selected bond lengths
and angles are given in Table 2. Crystallographic data for the
complexes have been deposited with the Cambridge Crystal-
lographic Data Centre (CCDC 891286 for 1 and 891284 for
2).
RESULTS AND DISCUSSION
Structure Description of the Complexes
SUPPLEMENTAL MATERIAL
Supplemental data for this article can be accessed on the
publisher’s website.
The molecular structures of the complexes 1 and 2 are shown
in Figures 1 and 2, respectively. The Ni atoms in the complexes
are coordinated by two phenolate O and two imine N atoms,
forming distorted square planar geometry. The distortion of the
coordination can be observed from the bond angles, ranging
from 82.2(3)◦ to 94.4(3)◦ (1) and 84.9(1)◦ to 94.7(1)◦ (2) for the
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